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WO2002038709A2 - Composition de carburant - Google Patents

Composition de carburant Download PDF

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Publication number
WO2002038709A2
WO2002038709A2 PCT/GB2001/004947 GB0104947W WO0238709A2 WO 2002038709 A2 WO2002038709 A2 WO 2002038709A2 GB 0104947 W GB0104947 W GB 0104947W WO 0238709 A2 WO0238709 A2 WO 0238709A2
Authority
WO
WIPO (PCT)
Prior art keywords
composition according
fuel composition
alcohol
fuel
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2001/004947
Other languages
English (en)
Other versions
WO2002038709A3 (fr
Inventor
Frank Bongart
William Hodgson
Alan Rae
Jürgen Röder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
O2Diesel Europe Ltd
Original Assignee
Cognis Deutschland GmbH and Co KG
AAE Technologies International PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB0027275A external-priority patent/GB0027275D0/en
Priority claimed from GB0027273A external-priority patent/GB0027273D0/en
Priority claimed from GB0027270A external-priority patent/GB0027270D0/en
Priority to ES01993664T priority Critical patent/ES2392402T3/es
Priority to HK04101060.9A priority patent/HK1059631B/en
Priority to AT01993664T priority patent/ATE516338T1/de
Priority to EP01993664A priority patent/EP1334170B1/fr
Priority to AU2002223789A priority patent/AU2002223789B2/en
Application filed by Cognis Deutschland GmbH and Co KG, AAE Technologies International PLC filed Critical Cognis Deutschland GmbH and Co KG
Priority to CA002436234A priority patent/CA2436234A1/fr
Priority to MXPA03004052A priority patent/MXPA03004052A/es
Priority to BR0115201-7A priority patent/BR0115201A/pt
Priority to AU2378902A priority patent/AU2378902A/xx
Priority to JP2002542029A priority patent/JP4118678B2/ja
Publication of WO2002038709A2 publication Critical patent/WO2002038709A2/fr
Publication of WO2002038709A3 publication Critical patent/WO2002038709A3/fr
Priority to US10/435,500 priority patent/US20040060226A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1826—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms poly-hydroxy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to fuel compositions which are free of alkanolamides and contain specific selected additives.
  • the invention furthermore relates to a process for the preparation of diesel oil/ethanol mixtures and the use of selected individual components as solubilisers for alcohol -containing diesel fuel.
  • British Patent GB 2 21 72 29 describes an additive which contains 48 parts by volume of an ethoxylated alcohol, 3 to 8 parts of lauric acid diethanolamide, 3 to 8 parts of oleic acid diethanolamide and 1.5 to 4 parts of an ethoxylated oleic acid.
  • Such compositions are suitable as additives which permit the dissolution of water in fuel and thus reduce the corrosion.
  • problems arise when, instead of the water, for example short-chain alcohols are to be used as the mixed phase with the fuels.
  • WO 98/17745 describes an alternative composition which contains 25% by volume of diethanolamide, 50% by volume of an ethoxylated alcohol and 25% by volume of a C ⁇ 4 fatty acid ethoxylated with 7 mol ethylene oxide per mole of fatty acid.
  • the additive is used for improving the solubility of ethanol in diesel, which in the end results in the reduction in the emissions of CO 2 and CO and NO x and particulate matter (PM) when the fuel is burned in a compression-ignition engine.
  • a fuel composition which is substantially free of alkanolamides, containing at least 95% by volume of a hydrocarbon-based fuel and from 0.1 to 5% by volume of an additive selected from the groups consisting of: a) the optionally alkoxylated linear or branched saturated or unsaturated monoalcohols having 8 to 24 C atoms, containing zero or 1 to 20 mol of ethylene oxide and/or 1 to 5 mol of propylene oxide per mol of alcohol, or b) the polyols having 2 to 6 carbon atoms, optionally partially esterified with fatty acids having 12 to 24 carbon atoms, or c) the alkoxylated fatty acids having 12 to 24 carbon atoms and 4 to 20 mol of ethylene oxide per mol of fatty acid, or d) the ethoxylated dimeric fatty acids.
  • an additive selected from the groups consisting of: a) the optionally alkoxylated linear or branched saturated or unsaturated monoalcohols having 8 to 24
  • fuels are understood as meaning all energy- supplying operating materials whose free combustion energy is converted into mechanical work. These include all types of motor and aviation fuels which are liquid at room temperature and atmospheric pressure.
  • Motor fuels for example for car or lorry engines, contain as a rule hydrocarbons, e.g. petrol fractions or higher- boiling mineral oil fractions.
  • Diesel fuels are obtained from gas oil by cracking or from tars which are obtained in the low-temperature carbonisation of lignite or hard coal.
  • Customary products have a density of between 0.83 and 0.88 g/cm 3 , a boiling point between 170 and 360°C and flash points between 70 and 100°C.
  • the hydrocarbon fuel may comprise any known hydrocarbon fuel or mixtures thereof, therefore such fuels include but shall not be limited to diesel, e.g. petroleum diesel or biodiesel, gasoline, aviation fuel, alcohol, etc.
  • the fuels according to the invention contain petroleum diesel or consist of petroleum diesel. They also include the so-called biodiesel, i.e. a fatty acid methyl ester, preferably the methyl ester of rape seed oil fatty acid.
  • the fuels according to the invention are distinguished by the fact that they contain only a single component selected from the classes a) to d) and that consequently no expensive and complicated mixtures of different individual substances are required.
  • the additive classes a) to d) used according to the invention are described in more detail below.
  • the fuel composition comprises component a).
  • Fatty alcohols are to be understood as a meaning primary aliphatic alcohols of the formula (I)
  • R 1 represents an aliphatic, linear or branched hydrocarbon radical having 8 to 24 carbon atoms and 0 and/or 1, 2 or 3 double bonds.
  • Typical examples are caproic alcohol, caprylic alcohol, 2-exthylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinly alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their industrial mixtures which are obtained, for example, in the high-pressure hydrogenation of industrial methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis and as a monomer fraction in the
  • Industrial fatty alcohols having 12 to 18 carbon atoms such as, for example, coconut fatty alcohol, palm fatty alcohol, palm kernel fatty alcohol or allow fatty alcohol, are preferred. Oleyl alcohol is particularly preferred. Guerbet alcohols having 12 to 16 carbon atoms are furthermore preferred.
  • alkoxylated, preferably ethoxylated and/or propoxylated derivatives of the fatty alcohols of the formula (J) is also particularly preferred.
  • the preparation of these compounds is known and is Carried out, for example, by reacting the fatty alcohols in the presence of acidic or basic catalysts with ethylene oxide and/or propylene oxide.
  • Preferred adducts contain 1 to 20 mol of ethylene and/or 1 to 5 mol of propylene oxide per mol of fatty acid.
  • Alkoxylated alcohols which contain 1 to 20 mol of ethylene oxide per mol of fatty alcohol and are free of propylene oxide are particularly preferred. It is furthermore preferable if the radical R represents unsaturated C ⁇ 2 - ⁇ s radical.
  • a fatty alcohol ethoxylated with 8 mol of ethylene oxide is to be regarded as a further particularly preferred compound a).
  • the fuel additive comprises component b).
  • polyols and their esterified derivatives are also suitable additives for the fuel according to the invention.
  • Polyols are organic compounds having 2 to 8 carbon atoms and 2 to 4 hydroxyl functions per molecule. These include, for example, ethylene glycol, propylene glycol, butylene glycol and their oligomers, for example butylene diglycol. Another preferably used polyol is glycerol.
  • neopentyl compounds such as pentaerythritol or trimethylolpropane, are suitable components for group b).
  • the partially esterified derivatives of the polyols for example glycerol mono-and/or diesters with fatty acids having 8 to 22 carbon atoms, are furthermore preferred.
  • Particularly preferred esters are pentaerythrityl esters partially esterified with the fatty acids.
  • Other derivatives such as ethers, for example diethylene glycol monobutyl ether, are also suitable.
  • the fuel additive comprises component c).
  • compositions according to the invention contain alkoxylated fatty acids as component c). These fatty acid alkoxylates are known compounds and can be prepared by all methods known to a person skilled in the art.
  • the fatty acid alkoxylates contained in the compositions according to the invention contain exclusively ethylene oxide groups as alkoxides. They preferably contain between 4 and 20 mol of ethylene oxide and in particular 2 to 10 mol of ethylene oxide per mol of ester.
  • the fatty acid components used are fatty acids have 5 to 30 C atoms and of natural or synthetic origin, in particular straight-chain, saturated or unsaturated fatty acids, including industrial mixtures thereof, as obtainable by lipolysis from animal and vegetable fats and oils, for example from coconut oil, palm kernel oil, soya oil, sunflower oil, colza oil, cottonseed oil, fish oil, beef tallow, and lard; specific examples are caprylic, capric, lauric, lauroleic, myristic, myristoleic, palmitic, palmitoleic, oleic, elaidic, arachic, gadoleic, behenic, and erucic acid.
  • the fuel additive comprises component d).
  • the oligomerisation of unsaturated fatty acids is a known electrocyclic reaction reported in review articles, for example by A. Behr in Fat Sci, Techno. 9 , 340 (1991), G. Spiteller in Fac Sci, Technol 94, 41 (1992) or P. Daute et al, in Fat Sci, Technol, 95, 91 (1993).
  • the oligomerisation on average two or three fatty acids combine and form dimers or trimers, which have predominantly cycloaliphatic structures.
  • a so- called monomer fraction is obtained, which contains unconverted starting materials and branched monomers which have been formed by isomerisation in the course of the reaction.
  • the oligomerisation can be carried out thermally or in the presence of noble metal catalysts.
  • the reaction is carried out in the presence of clays, such as, for example, montmorillonite.
  • the content of dimers and trimers or the amount of monomer fraction can be regulated by the reaction conditions.
  • Industrial mixtures can finally also be purified by distillation.
  • Suitable starting materials for the oligomerisation are industrial unsaturated fatty acids having 12 to 22, preferably 16 to 18, carbon atoms.
  • Typical examples are palmitoleic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, conjuenic fatty acid, elaeostearic acid, ricinoleic acid, gadoleic acid, erucic acid, and their industrial mixtures with saturated fatty acids.
  • suitable industrial mixtures are unhydrogenated cleavage fatty acids or natural triglycerides having iodine numbers in the range from 40 to 140, such as, for example, palm oil acid, tallow fatty acid, colza fatty acid, sunflower fatty acid and the like. Cleavage fatty acids having a higher content of oleic acid are preferred.
  • esters preferably methyl esters. It is also possible to oligomerise the acid and to convert it into the methyl esters prior to hydrogenation. The conversion of the ester group into the acid group takes place in a manner known per se.
  • Dimeric fatty acids which are particularly preferred in the context of the present invention, are obtained by oligomerisation of industrial oleic acid and preferably have a dimer content of 50 to 99% by weight and a polymer content (including trimer content) of 1 to 50% by weight.
  • the content of monomers may be 1 to 15% by weight and, if required, may be reduced by distillation.
  • Dimeric fatty acids which are obtained by oligomerisation are industrial oleic acid and have a dimer content of 70 to 85% by weight, a polymer content of 10 to 20% by weight and a monomer content of 5 to 15% by weight are particularly preferred.
  • the percentages by weight are based on the total amounts of dimeric fatty acid.
  • the additive components a) to d) are preferably chosen so that their HLB value is less than 12.
  • the hydrocarbon-based fuel may include an amount of an alcohol or alcohols.
  • Such alcohols are preferentially Cl to C6 alkanols, such as propanol, butanol or ethanol, and isomers thereof.
  • the most preferred alcohol is ethanol.
  • the hydrocarbon-based fuel comprises an alcohol
  • the amount of alcohol present may vary, but is preferably present in an amount of from 1 to 10% by volume.
  • the fuel composition of the invention may comprise at least 85% by volume of a hydrocarbon-based fuel, from 1 to 10%) by volume of an alcohol, such as ethanol and from 0.1 to 5% by weight of an additive selected from the groups a), b), c) and d).
  • the fuel compositions according to the invention are prepared by mixing the components a), b), c) or d) individually with a fuel/ethanol mixture.
  • Preferred fuel compositions are those in which the volume ratio (v/v) of fuel, e.g. petroleum diesel to additive is in the range of 1000:0.5 to 1000:50, and preferably of 1000:1 to 1000:50.
  • a fuel composition consisting of 90 to 94.5% by volume of diesel oil, 5 to 8 % by volume of alcohol, e.g. ethanol and 0.5 to 2% by volume of an additive a), b), c) or d) according to the above description.
  • the use of the additives according to the invention makes it possible to prepare mixtures of fuels with alcohol, e.g. ethanol, preferably petroleum diesel with ethanol, in an economical manner.
  • alcohol e.g. ethanol
  • a maximum of 0.5 to 2.0% by volume of additive are added to the diesel oil/ethanol mixture.
  • Water may also be present. It is particularly preferable to use substantially anhydrous ethanol which preferably contains less than 0.5 % by volume of water.
  • the total fuel composition is preferably anhydrous, i.e. the water content should be less than 0.2 % volume, preferably less than 0.11% by volume.
  • a further aspect of the present invention relates to a fuel composition consisting of 88 to 98.5% by volume of diesel oil, 1 to 10% by volume of alcohol, e.g. ethanol and 0.5 to 2% by volume of an additive a), b), c) or d) according to the above description.
  • ethanol may be produced from fossil fuel feedstocks or by fermentation of sugars derived from grains or other biomass materials. Therefore, ethanol suitable for use in accordance with the fuel compositions of the invention may be fuel grade ethanol derived from yeast or bacterial fermentation of starch-based sugars. Such starch-based sugars may be extracted from corn, sugarcane, tapioca and sugar beet. Alternatively, fuel grade ethanol may be produced via known dilute and/or concentrated acid and/or enzymatic hydrolysis of a particular biomass material, for example, from waste industrial sources include, cellulosic portions of municipal solid waster, waste paper, paper sludge, saw dust. Biomass may also be collected from agricultural residues included, for example, rise husks and paper- mill sludge.
  • a suitable fuel grade ethanol for use in accordance with the invention may contain none or only contaminant levels of water. It should be noted that fuels containing, e.g. ethanol, may contain trace amounts of water. Thus, for example, anhydrous ethanol will generally contain up to 0.5% w/w of water. Therefore, hereinafter reference to an anhydrous fuel composition should be understood be a composition which is substantially free of water, but may contain, for example, up to 0.5% w/w of water. Alternatively, a suitable fuel grade ethanol for use in accordance with the invention may contain higher amounts of water, up to 5% w/w (hydrous ethanol).
  • ethanol in combination with a diesel fuel has previously posed problems wherein the ethanol/diesel fuel mixture would undesirably separate into two distinct phases, especially when water is present, and render the resultant mixture unsuitable for use as a combustible fuel.
  • the use of the fuel additives of the invention permits hydrous ethanol to be blended satisfactorily with conventional diesel fuel without forming two phases.
  • the use of fuel grade ethanol blended in accordance with the invention imparts desirable combustion characteristics to the overall fuel composition; such as improved fuel stability, lower smoke and particulate matter, lower CO and NOx emissions, improved antiknock characteristics, and/or improved anti-freeze characteristics.
  • the presence of the additive of the invention ensures that the fuel composition forms a consistent stable homogenous composition and creates a monolayer simultaneously a result of which leads to a better more complete burn which reduced pollution and increases miles per gallon.
  • a water soluble alcohol a C6 to C12 alcohol a C6 to C18 ethoxylated alcohol a CIO to C24 fatty acid, and a nitrogen source.
  • the fuel composition of the invention can comprise very low fuel: additive ratios in combination with nitrogenous compounds, such as urea.
  • nitrogenous compounds such as urea.
  • the nitrogen compound may be selected from the group consisting of ammonia, hydrazine, alkyl hydrazine, dialkyl hydrazine, urea, ethanolamine, mono alkyl ethanolamine, and dialkyl ethanolamine wherein alkyl is independently selected from methyl, ethyl, n-propyl or isopropyl. Urea is preferred.
  • the nitrogen compound may be an anhydrous compound or a hydrous compound, e.g. an aqueous solution, and may be up to a 5% w/w aqueous solution.
  • a method of solubilising a nitrogen compound in a fuel composition which comprises mixing a hydrocarbon fuel, a nitrogen compound and a fuel additive as hereinbefore described.
  • the method of the invention may optionally include the addition of an alcohol, such as ethanol or water, as hereinbefore described.
  • the nitrogen compound may be added by being incorporated into the fuel additive or may be added separately. Furthermore, the nitrogen compound may be added as an aqueous solution.
  • the fuel composition of the invention may also optionally comprise a cetane booster in amount of from 0.1% v/v to 1.0% v/v, based on the volume of the mixture.
  • a cetane booster is included in the fuel composition of the invention it may be added as part of the fuel additive of the invention or it may be added separately.
  • a suitable cetane booster for use in the mixture is selected from the group comprising, 2-ethylhexyl nitrate, tertiary butyl peroxide, diethylene glycol methyl ether, cyclohexanol, and mixtures thereof.
  • the amount of cetane booster present in the mixture is a function of the cetane value of the particular diesel fuel and the amount of ethanol present in the particular fuel composition. Generally, the lower the diesel fuel cetane value, the higher the amount of the cetane booster, similarly, because ethanol typically acts as a cetane depressant, the higher the concentration of ethanol in the solution, the more cetane booster may be necessary in the mixture.
  • the fuel additives of the invention are advantageous in that, ter alia, they are more efficient at producing micro emulsions than prior art additives. Therefore, they are capable of more efficiently producing a stable, clear and homogenous solution with a hydrocarbon fuel, e.g. diesel/ethanol, even in the presence of water. Therefore, according to a further feature of the invention we provide a fuel composition as hereinbefore described, which optionally includes an amount of water, and wherein the fuel consists of a substantially stable, clear and substantially homogeneous solution.
  • the fuel additive or the fuel composition of the invention may also optionally include a demulsifier in an amount of less than 5% v/v and preferably less than 1% v/v based on the volume of the mixture.
  • CFPP cold filter plugging point test
  • the additive-containing fuel was cooled stepwise to - 30°C for this purpose, in each case a sample being taken at 1°C temperature intervals and being sucked through a standardised filter means at reduced pressure of 2 kPa.
  • the stated temperature value then corresponds to the temperature at which the fuel can no longer flow through the filter means in a specified time.
  • Typical of the results obtained for compounds of the invention was oleyl alcohol + 4.6 EO which gave a CFPP value of -18°C which corresponds to the value for diesel without additives.
  • An additive composition was made up ethoxylated oleic acid and 1% by volume of this composition was added to 7.7% ethanol/92.3% diesel blends, including certification diesel, US No 1 (10% aromatic) diesel containing 0.1 % cetane improver, resulting in optically clear and stable micro-emulsion fuels. These were tested as automotive fuels on a 1991 Detroit Diesel Series 60 engine using the EPA (USA Environmental Protection Agency) heavy duty engine certification test as described in the Code of Federal Regulations, Title 40, Part 86, Subpart N.
  • Toxic exhaust gas omissions were measured and compared with those of the base un-additised diesel. Significant reductions were obtained of toxic gases CO, CO 2 , NOx and particulate matter.
  • the prior art additive contained 25% diethanolamide, 50% 0 ethoxylated C9-11 alcohol and 25% of a C14 fatty acid ethoxylated with 7 moles EO.
  • ethanol/diesel blends were made up with water contents up to 0.6%v/v and the amount of additive required to produce clear, stable solutions determined volumetrically.
  • solubilising ratio i.e. the volume of prior art additive divided by the volume of the additive of the invention, was plotted against water content (see fig.l). The results confirm that the additive of the invention is considerably more effective especially at low water concentrations.
  • a Blend was made of certification diesel, biodiesel and ethanol stabilised with the surfactant additive described in Example 1. Engine exhaust emission tests showed reductions in CO, NOx and particulate matter compared with the base diesel.
  • Example A solution of 0.25% urea in ethanol was blended in a 7.7:92.3 ratio with US No 1 diesel and 1.0% of additive was added to produce a clear micro- emulsion automotive fuel. Tests using this blend showed that toxic gas emissions were again lower than the base fuel, the urea having made a contribution to the reductions obtained.
  • Blends were made up of EPA and CARB gasolines with various amounts of ethanol e.g. a typical blend contained 90% v/v gasoline and 10% ethanol. Small amounts, typically 1% v/v of the additive of the invention were added to the gasoline/ethanol blends and the resulting fuels tested as automotive fuels and the exhaust emissions compared with those of the base gasolines. The results confirmed that ethanol/gasoline blends combust to give lower levels of toxic gas emissions.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

L'invention concerne une composition de carburant sensiblement exempte d'alcanolamides, renfermant au moins 95 % en volume d'un carburant à base d'hydrocarbone et entre 0,1 et 5 % en volume d'un agent additif sélectionné parmi les groupes comprenant: a) les monoalcools éventuellement alcoxylés linéaires ou ramifiés saturés ou insaturés présentant entre 8 et 24 atomes C, comprenant zéro ou 1 ou 20 mol d'oxyde d'éthylène et/ou entre 1 et 5 mol d'oxyde de propylène par mol d'alcool, ou b) les polyols présentant entre 2 et 6 atomes de carbone, éventuellement partiellement estérifiés au moyen d'acides gras présentant entre 12 et 24 atomes de carbone, ou c) les acides gras alcoxylés présentant entre 12 et 24 atomes de carbone et entre 4 et 20 mol d'oxyde d'éthylène par mol d'acide gras, ou d) les acides gras dimères éthoxylés.
PCT/GB2001/004947 2000-11-08 2001-11-08 Composition de carburant Ceased WO2002038709A2 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
BR0115201-7A BR0115201A (pt) 2000-11-08 2001-11-08 Composição de combustìvel, processo para a preparação da mesma, método de funcionamento de um motor de combustão interna, e, usos de monoálcoois, de polióis, de ácidos graxos, e de ácidos graxos diméricos etoxilados
AU2378902A AU2378902A (en) 2000-11-08 2001-11-08 Fuel composition
JP2002542029A JP4118678B2 (ja) 2000-11-08 2001-11-08 燃料組成物
MXPA03004052A MXPA03004052A (es) 2000-11-08 2001-11-08 Aditivos de combustible libres de alcanolamida.
AT01993664T ATE516338T1 (de) 2000-11-08 2001-11-08 Brennstoffzusammensetzung
EP01993664A EP1334170B1 (fr) 2000-11-08 2001-11-08 Composition de carburant
AU2002223789A AU2002223789B2 (en) 2000-11-08 2001-11-08 Fuel composition
ES01993664T ES2392402T3 (es) 2000-11-08 2001-11-08 Composición de combustible
CA002436234A CA2436234A1 (fr) 2000-11-08 2001-11-08 Composition de carburant
HK04101060.9A HK1059631B (en) 2000-11-08 2001-11-08 Fuel composition
US10/435,500 US20040060226A1 (en) 2000-11-08 2003-05-08 Alkanolamide free fuel additives

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB0027275A GB0027275D0 (en) 2000-11-08 2000-11-08 Fuels
GB0027273.2 2000-11-08
GB0027275.7 2000-11-08
GB0027270A GB0027270D0 (en) 2000-11-08 2000-11-08 Fuels
GB0027270.8 2000-11-08
GB0027273A GB0027273D0 (en) 2000-11-08 2000-11-08 Fuels

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US10/435,500 Continuation US20040060226A1 (en) 2000-11-08 2003-05-08 Alkanolamide free fuel additives

Publications (2)

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WO2002038709A2 true WO2002038709A2 (fr) 2002-05-16
WO2002038709A3 WO2002038709A3 (fr) 2003-02-06

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EP (1) EP1334170B1 (fr)
JP (1) JP4118678B2 (fr)
CN (1) CN1551912A (fr)
AT (1) ATE516338T1 (fr)
AU (2) AU2002223789B2 (fr)
BR (1) BR0115201A (fr)
CA (1) CA2436234A1 (fr)
ES (1) ES2392402T3 (fr)
MX (1) MXPA03004052A (fr)
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WO2009035551A1 (fr) 2007-09-12 2009-03-19 Martek Biosciences Corporation Huiles biologiques et leur production et utilisations
DE102008032254A1 (de) * 2008-07-09 2010-01-21 Man Nutzfahrzeuge Ag Rußarme Dieselkraftstoffe, enthaltend einen Kraftstoffzusatz, deren Verwendung sowie die Verwendung des Kraftstoffzusatzes zur Herstellung von rußarmen Dieselkraftstoffen
WO2010053354A3 (fr) * 2008-11-05 2010-11-04 Criss Cross Technology Bv Additif de carburant moteur ayant des propriétés améliorées et procédés de fabrication de cet additif
WO2011082190A1 (fr) 2009-12-28 2011-07-07 Martek Biosciences Corporation Thraustochytrides recombinants qui se développent sur le saccharose, compositions les contenant, leurs procédés de préparation, et leurs utilisations
US8974553B2 (en) 2012-03-29 2015-03-10 Joseph Ried Miscible diesel fuel ethanol composition
EP2891698A1 (fr) * 2014-01-03 2015-07-08 Arkema France Composition de carburant d'aviation
EP2982734A1 (fr) * 2014-08-01 2016-02-10 Ekobenz So. z o. o. Mélange de carburant, en particulier pour des moteurs à allumage par étincelle

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Publication number Priority date Publication date Assignee Title
GB2451507A (en) * 2007-08-03 2009-02-04 O2 Diesel Europ Ltd Fuel additive
WO2009035551A1 (fr) 2007-09-12 2009-03-19 Martek Biosciences Corporation Huiles biologiques et leur production et utilisations
US9453172B2 (en) 2007-09-12 2016-09-27 Dsm Ip Assets B.V. Biological oils and production and uses thereof
DE102008032254A1 (de) * 2008-07-09 2010-01-21 Man Nutzfahrzeuge Ag Rußarme Dieselkraftstoffe, enthaltend einen Kraftstoffzusatz, deren Verwendung sowie die Verwendung des Kraftstoffzusatzes zur Herstellung von rußarmen Dieselkraftstoffen
DE102008032254B4 (de) * 2008-07-09 2010-10-21 Man Nutzfahrzeuge Ag Rußarme Dieselkraftstoffe, enthaltend einen Kraftstoffzusatz, deren Verwendung sowie die Verwendung des Kraftstoffzusatzes zur Herstellung von rußarmen Dieselkraftstoffen
WO2010053354A3 (fr) * 2008-11-05 2010-11-04 Criss Cross Technology Bv Additif de carburant moteur ayant des propriétés améliorées et procédés de fabrication de cet additif
WO2011082190A1 (fr) 2009-12-28 2011-07-07 Martek Biosciences Corporation Thraustochytrides recombinants qui se développent sur le saccharose, compositions les contenant, leurs procédés de préparation, et leurs utilisations
US8974553B2 (en) 2012-03-29 2015-03-10 Joseph Ried Miscible diesel fuel ethanol composition
EP2891698A1 (fr) * 2014-01-03 2015-07-08 Arkema France Composition de carburant d'aviation
US9528058B2 (en) 2014-01-03 2016-12-27 Arkema France Aviation fuel composition
EP2982734A1 (fr) * 2014-08-01 2016-02-10 Ekobenz So. z o. o. Mélange de carburant, en particulier pour des moteurs à allumage par étincelle

Also Published As

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ATE516338T1 (de) 2011-07-15
CA2436234A1 (fr) 2002-05-16
WO2002038709A3 (fr) 2003-02-06
JP4118678B2 (ja) 2008-07-16
EP1334170B1 (fr) 2011-07-13
EP1334170A2 (fr) 2003-08-13
JP2004520454A (ja) 2004-07-08
BR0115201A (pt) 2004-02-03
US20040060226A1 (en) 2004-04-01
ES2392402T3 (es) 2012-12-10
HK1059631A1 (en) 2004-07-09
MXPA03004052A (es) 2005-04-11
CN1551912A (zh) 2004-12-01
AU2002223789B2 (en) 2007-03-01
AU2378902A (en) 2002-05-21

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